Fiber reactive photochromic dyes

ABSTRACT

PROCESS OF DYEING A TEXTILE MATERIAL CONTAINING REACTIVE HYDROGEN ATOMS, E.G., NYLON, WHICH COMPRISES APPLYING AS DISPERSED DYES, FIBER-REACTIVE DYE COMPOUNDS COMPRISING PHOTOCHROMIC MERCURY DITHIZONATES CONTAINING FIBER-REACTIVE GROUPS TO SAID TEXTILE MATERIAL FROM AN AQUEOUS DISPERSION AND SUBSEQUENTLY FIXING THE DYE WITH AN ALKALI AFTER-TREATMENT. THE DYED MATERIALS EXHIBIT PHOTOCHROMIC PROPERTIES.

United States Patent C 3,578,389 FIBER REACTIVE PHOTOCHROMIC DYES JohnKazan, Jr., Somerville, and Walter Henry Foster, Jr., Freehold, N.J.,assignors to American Cyanamid Company, Stamford, Conn. N Drawing.Original application Jan. 26, 1967, Ser. No. 611,840, now Patent No.3,505,306, dated Apr. 7, 1970. Divided and this application June 3,1969, Ser.

Int. Cl. D069 1/10 US. Cl. 8-163 Claims ABSTRACT OF THE DISCLOSUREProcess of dyeing a textile material containing reactive hydrogen atoms,e.g., nylon, which comprises applying as dispersed dyes, fiber-reactivedye compounds comprising photochromic mercury dithizonates containingfiber-reactive groups to said textile material from an aqueousdispersion and subsequently fixing the dye with an alkaliafter-treatment. The dyed materials exhibit photochromic properties.

This application is a divisional of copending application Ser. No.611,840, filed Jan. 26, 1967, now US. Pat. No. 3,505,306.

This invention relates to a new class of fiber-reactive photochromic dyecompounds. It also relates to a process of applying these compounds tofibrous textile materials containing reactive hydrogens, such as nylon,and to the dyed materials, per se.

The new fiber-reactive dye compounds of the invention are derivatives ofmercuric complexes of diaryl thiocarbazones which correspond to theformula:

wherein Q is a divalent aromatic radical, such as phenylene, tolylene,naphthylene, etc., A is an aryl radical, such as phenyl or naphthyl, X,Y and Z are individually hydrogen, lower alkyl, lower alkoxy, halo,nitro or di-lower alkylamino radicals, and M is a fiber-reactive moietyseected from the group consisting of:

3,578,389 Patented May 11, 1971 It has been found in accordance withthis invention that the dye compounds can be applied as disperse dyes toanimal fibers, such as wool and silk, to cellulose ester fibers and tosynthetic fibers, such as nylon, and that the fixation of the dyes onthe fibers is increased by an aftertreatment with alkali as shownhereafter.

The new fiber-reactive dye compounds of the present invention (FormulaI) can be made by the following procedures: (a) Dichloroanddibromo-s-triazinylamino compounds are obtained by reacting one mole ofan aminoarylrnercuric complex of a diaryl thiocarbazone, represented bythe formula:

where Q, A and X, Y and Z have the same meanings as in Formula I, withone mole of cyanuric chloride or bromide, the said mercuric complex (ofFormula II) having first been prepared by reaction of a diarylthiocarbazone with an aminoarylmercuric acetate or halide. Monochloroandmonobromo-s-triazinylamino compounds are obtained by reacting one moleof the aminoarylmercuric complex of [Formula II with one mole of adichloroor dibromo-s-triazine of the formula:

o LY

where the Xs are chloro or bromo atoms and Y is alkyl, aryl, amino, anorganic radical containing N, O or S linkage to the triazine ring, orNH-D.

(b) Monoand dichloro and -bromopyrimidinylamino compounds are obtainedby reacting one mole of the aminoarylmercuric complex of Formula II withone mole of a halopyrimidine containing at least two chlorine or bromineatoms in the 2-, 4- and 6-positions.

(c) Chloroacetylamino compounds are obtained by reacting one mole of theaminoarylmercuric complex of Formula II with one mole of chloroacetylchloride.

(d) Beta-chloropropionylamino compounds are obtained by reacting onemole of the aminoarylmercuric complex of Formula II with one mole ofbeta-chloropropionyl chloride. By then eliminating hydrogen chloride,the corresponding acrylarnide derivatives, which are also useful in thisinvention, are obtained.

(e) Beta-chloroethylsulfonyl compounds are obtained by reacting a diarylthiocarbazone with a beta-chloroethylsulfonylarylmercuric chloride.

(f) Beta-sulfatoethylsulfonyl compounds are obtained by reacting adiaryl thiocarbazone with a beta-sulfatoethylsulfonylarylmercuricchloride.

(g) Vinylsulfonyl compounds are obtained by reacting a diarylthiocarbazone with a vinylsulfonylarylmercuric chloride.

(h) N-(beta-chloroethyl)sulfamoyl compounds are obtained by reacting adiaryl thiocarbazone with an N- (beta-chloroethyl)sulfamoylarylmercuricchloride.

(i) N-(beta-sulfatoethyl)sulfamoyl compounds are obtained by reacting adiaryl thiocarbazone with an N- (beta-sulfatoethyl)sulfamoylarylmercuric chloride.

(j) Methylolated N,N bis(beta-carbamoylethyl)sulfamoyl compounds areobtained by reacting N,N-bis (betacarbamoylethyl)sulfamoyl compoundswith formaldehyde, the carbamoyl compounds having been prepared byreaction of a diaryl thiocarbazone with anN,N-bis(betacarbamoylethyl)sulfamoylarylmercuric chloride.

The substituted arylmercuric salts are obtainable by conventionalprocedures, such as reaction of a substituted aryl compound withmercuric acetate or reaction of a substituted aryldiazonium salt withmercuric chloride and cuprous chloride.

The reaction of a diaryl thiocarbazone with a substituted arylmercuricsalt is typically exemplified by the reaction of diphenylthiocarbazone(III) and p-aminophenylmercuric acetate (IV) to give(p-aminophenyl)mercuric dithizonate (11a).

H5 (Ha) Reaction (1) is conveniently effected at room temperature in atwo-phase solvent medium, such as a mixture of chloroform and water, andin the presence of a buffer, such as sodium bicarbonate.

The reaction of an aminoarylmercuric complex of a diaryl thiocarbazonewith a cyanuric halide, dihalo-striazine, polyhalopyrimidine,chloroacetyl chloride or betachloropropionyl chloride is typicallyexemplified by the reaction of (p-aminophenyl)mercuric dithizonate (Ila)with cyanuric chloride (V) to give the fiber reactive compoundp-[(4,6-dichloro-s-triazin 2 yl)amino]phenylmercuric dithizonate (la).

Reaction (2) is conveniently effected in a suitable solvent, such asacetone, and in the presence of a buffer, such as sodium bicarbonate.The reaction is carried out at room temperature or below. Higherreaction temperatures can be used when mono-halo products are desired.

Dihalo-s-triazines which may be used include 2,4- dichloro 6phenoxy-s-triazine, 2,4-dichloro-6-phenyls-triazine, ,4-dichloro 6methyl-s-triazine, 2,4-dichloro- 6-methylthio-s-triazine, 2,4-dichloro 6methylamino-s triazine, etc.

Halopyrimidines which may be used include 2,4,6-trichloropyrimidine,2,4,6 tribromopyrimidine, 2,4,5-tri chloropyrimidine,2,4-dichloro-6-methylpyrimidine, 2,4-dichloro-6-methoxyprimidine, 2,4dichloro 6 phenylpyrimidine, etc.

The compounds of this invention are applied to textile materialscontaining reactive hydrogen by well-known procedures for applying fiberreactive dyes to such fibers. Suitable textile materials for use includethose containing various synthetic fibers such as nylon and otherpolyamide types, cellulose esters such as cellulose acetate, and animalfibers such as Wool and silk, etc. The dyeings are made by proceduresused for disperse dyes. The wet fastness of the dyeings is improved byan aftertreatment with alkali.

The dyeings are advantageously made by immersing the textile material inaqueous dispersions of the fiber reactive compounds at the boil orslightly below, for 15-60 minutes. The dispersions are convenientlyprepared by dissolving the dye in a water-miscible solvent, such asacetone, and adding the solution to water containing a small amount of asurface active agent, i.e., a dispersing agent, such as a long chainalkyl sulfate.

The alkaline aftertreatment whereby the fixation of the dye isincreased, is effected by immersing the dyed fabric in aqueous alkali.Suitable alkalies include sodium hydroxide, potassium hydroxide, lithiumhydroxide, sodium carbonate, potassium carbonate, soap and the like.Sufficient alkali is used to neutralize all of the hydrogen chloridewhich theoretically could be evolved and still keep the mixturealkaline. It is advantageous to carry out the alkali treatment at theboil.

The dyes are thus firmly bound to, and are an integral part of, thetextile material. In other words, there has been reaction of thederivative of the arylmercuric com pleX of a diaryl thiocarbazone withthe active-hydrogencontaining textile material.

The fabrics thus dyed have photochromic properties. In the case of thedichlorotriazinylaminophenylmercuric complex of diphenyl thiocarbazone,the color changes from orange to blue when the fabric is irradiated withsunlight or other source of light. It will be appreciated that theretention by the dye of this property, even though it is bound to thefabric through the fiber reactive linkage, is most surprising since thecolor change involves a drastic alteration in the configuration of themolecule. Thus, though not conclusive, the evidence indicates acis-trans isomerization and tautomeric shift in the photochromic portionof the molecule, as follows.

While Blue (1) is considered the more likely, it is possible that thestructure of the blue form might also be either (2) or (3) as follows.

The invention is illustrated by the following examples in which theparts and percentages given are by weight.

EXAMPLE 1 (pAminophenyl)mercuric dithizonate s -C=NNI-IC H To avigorously stirred mixture of about 150 parts chloroform and parts Waterthere was added 5 parts (0.0142 mole) p-aminophenylmercuric acetate,3.78 parts (0.045 mole) sodium bicarbonate and 3.33 parts (0.013

mole) diphenylthiocarbazone in portions. The mixture changed color frompurple to orange. After stirring for 15 minutes, the chloroform wasevaporated under reduced pressure and the product was isolated byfiltration. Recrystallization from acetone gave 3 parts of fine orangeneedles, M.P. 191.5192.5 C. Recovery from the mother liquor increasedthe total yield to 4 parts.

Calcd. for C H HgN S (percent): C, 41.6; H, 3.13; Hg, 36.6; N, 12.8; S,5.85. Found (percent): C, 42.0; H, 3.06; Hg, 36.6; N, 12.9; S, 5.81.

EXAMPLE 2 p- (4,6-dichloro-s-triazin-2-yl) amino] phenylmercuricdithizonate To a solution of 0.5 part (0.00091 mole) of the product ofExample 1 in about 80 parts acetone and parts water at -2 C., there wasadded with stirring 0.153 part (0.00182 mole) sodium bicarbonate and0.168 part (0.00091 mole) cyanuric chloride. The resulting solution wasstirred for minutes at 2 C., and then poured into a mixture of 200 partsice and 300 parts water. Filtration gave 0.7 part of product which,after recrystallization from acetone, appeared as orange-red crystalsmelting at 126.5-127.5 C.

Calcd. for C H Cl HgN S (percent): C, 37.9; H, 2.32; Cl, 10.2; Hg, 28.8;N, 16.1; S, 4.61. Found (percent): C, 37.9; H, 2.17; Cl, 9.84; Hg, 28.5;N, 16.6; S, 4.41.

The corresponding p-[(dichloropyrimidinyl)amino]- phenylmercuricdithizonate, p-(chloroacetylamino)phenylmercuric dithizonate andp-(beta-chloropropionylamino)phenylmercuric dithizonate are obtainedwhen the above procedure is repeated substituting equivalent amounts of2,4,6-trichloropyrimidine, chloroacetyl chloride andbeta-chloropropionyl chloride, respectively, for the cyanuric chlorideused therein.

EXAMPLE 3 p- [N- (beta-chloroethyl) sulfamoyl] phenylmercuricdithizonate The procedure of Example 1 is repeated substituting anequivalent amount of p-[N-(beta-chloroethyl)sulfamoyl]phenylmercuricchloride (prepared from the corresponding phenyldiazonium chloride byreaction with mercuric chloride and cuprous chloride) for thep-aminophenylmercuric acetate.

The corresponding p-substituted phenylmercuric dithizonates are obtainedwhen the above procedure is repeated 'with substitution ofp-(beta-chloroethylsulfonyl)- phenylmercuric chloride,p-(beta-sulfatoethylsulfonyl)- phenylmercuric chloride,p-(vinylsulfonyl)phenylmercuric chloride,p-[N-(beta-sulfatoethyl)sulfamoyl]phenylmercuric chloride orp-[N,N-bis(beta carbamoylethyD- sulfamoyl]phenylmercuric chloride forthe p-[N-(betachloroethyl)sulfamoyl]phenylmercuric chloride. Reaction ofthe p-[N,N-bis(beta-carbamoylethyl)sulfamoyl] phenylmercuric dithizonatewith an excess of formaldehyde under mildly alkaline conditions providesthe desired methylolatedp-[N,N-bis(beta-carbamoylethyl)sulfamoyl]phenylmercuric dithizonate.

APPLICATION AND EVALUATION 1% Dye 5% Duponol WA to 1 Liquor to fabricratio Dyeing was carried out for 30 minutes at the boil. Compound 1produced a red shade on the nylon while the dyeing of 2 was orange.Portions of each fabric were then treated for 10 minutes at the boilwith:

(a) neutral soap solution (b) pH 10 Na CO solution (alkaline fixingbath).

The untreated, soaped and alkaline fixed fabrics were each extracted forone hour in boiling n-propanol. The percent dye remaining on the variousfabrics was then estimated from visible reflectance curves. Reflectancespectra were obtained using a recording spectrophotometer. The resultsare presented in Table I.

TABLE I.DYEING ON NYLON Relative Relative percent percent compoundcompound Treatment Ex. of Ex. 2

Untreated, unextracted. 100 Untreated, extracted- 4 34 Soaped, extracted5 53 Alkaline fixed, extracted 6 55 These results show that essentiallyall of the unreactive compound of Example 1 was removed by theextraction with n-propanol, while a substantial portion of the reactivecompound of Example 2 remained fixed after the extraction. The data showthat some of the reactive compound reacted with the fabric during thedyeing procedure and additional fixation occurred during the soaping andalkaline treatments.

Essentially similar results are obtained with nylon dyeings utilizing,in place of triazinyl derivative of Example 2, any one of the otherderivatives of the mercuric complexes of diaryl thiocarbazones embracedby Formula I.

Upon exposure to bright sunlight, the color of the alkaline-fixed,extracted dyeing with the compound of Example 2 changed from theoriginal orange, through various shades of gray, to a final dull blue.When removed from the sunlight the color returned to the originalorange. The time required for this return is dependent on such factorsas ambient light level, the temperautre of the fabric and its moisturecontent. Thus, soaking the fabric in water causes a very rapid return tothe original orange color. It is, therefore, seen that the photochromicproperties of the dye is retained even though the dye is bound to thefiber through the newly introduced fiber-reactive linkage.

While the present invention has been discussed and illustrated herein,in terms of specific examples and embodiments thereof, it is notintended that the scope of the invention be limited in any way thereby,except as defined in the accompanying claims.

We claim:

1. A process of dyeing a textile material containing reactive hydrogenatoms comprising immersing said material in a dye bath comprising anaqueous dispersion of a compound represented by the formula wherein Q isa divalent aromatic radical selected from the group consisting ofphenylene, tolylene and naphthylene, A is aryl radical selected from thegroup consisting of phenyl and naphthyl, X, Y and Z are individuallyhydrogen, lower alkyl, lower alkoxy, halo, nitro or dilower alkylaminoradicals and M is where X is chloro or bromo, Y is chloro, bromo, alkyl,amino, an organic radical containing N, O or S linkage to the triazinering or NHD,

wherein Q is a divalent aromatic radical selected from the groupconsisting of phenylene, tolylene and naphthylene, A is aryl radicalselected from the group consisting of phenyl and naphthyl, X, Y and Zare individually hydrogen, lower alkyl, lower alkoxy, halo, nitro ordi-lower alkylamino radicals and M is ---NHC c-Y where X is chloro orbromo, Y is chloro, bromo, alkyl, amino, an organic radical containingN, O or S linkage to the triazine ring or NH-D,

5. Nylon dyed with p-[(4,6-dichloro-s-triazin-Z-yl)- amino]phenylmercuric dithizonate.

References Cited UNITED STATES PATENTS 3,359,254 12/1967 Kazan 2601493,505,306 4/1970 Kazan et al 260-146 GEORGE F. LESMES, Primary ExaminerT. J. HERBERT, JR., Assistant Examiner US. Cl. X.R. 8178

